CN108352211A - Electroconductive paste and conductive trace or coating - Google Patents
Electroconductive paste and conductive trace or coating Download PDFInfo
- Publication number
- CN108352211A CN108352211A CN201680065684.0A CN201680065684A CN108352211A CN 108352211 A CN108352211 A CN 108352211A CN 201680065684 A CN201680065684 A CN 201680065684A CN 108352211 A CN108352211 A CN 108352211A
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- China
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- weight
- electroconductive paste
- inorganic particle
- particle mixture
- inorganic
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- 239000011248 coating agent Substances 0.000 title claims abstract description 19
- 238000000576 coating method Methods 0.000 title claims abstract description 19
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- 239000010954 inorganic particle Substances 0.000 claims abstract description 145
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- 239000000758 substrate Substances 0.000 claims abstract description 48
- 239000007787 solid Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000004020 conductor Substances 0.000 claims abstract description 31
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- 239000002562 thickening agent Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to the electroconductive pastes for forming conductive trace or coating on substrate, especially suitable for solar cell.The paste includes the solid portion being dispersed in organic media, and the solid portion includes conductive material and inorganic particle mixture, wherein the inorganic particle mixture includes the particle of basic crystalline state.The invention further relates to prepare the method for electroconductive paste, the method for surface electrode for manufacturing solar cell, for the electrode and solar cell of solar cell.
Description
Technical field
The present invention relates to the methods that these are pasted particularly suitable for the electroconductive paste and manufacture in solar cell, are related in example
Method as manufactured conductive trace or coating in solar cell surface, and be related to the conductive trace or painting being formed on
The surface of the solar cell of layer.
Background technology
Conduction (such as silver) paste of silk-screen printing is typically used as the conductive trace of solar cell such as silicon solar cell.Institute
It states paste and generally comprises conduction (such as silver) powder being all dispersed in organic media, frit and sometimes one or more another
Outer additive.Frit has several effects.In sintering procedure, it becomes melting behaviors, and therefore plays conductive trace
It is adhered to the effect of semiconductor die on piece.However, etching away antireflection or the passivation layer being arranged on a surface of a semiconductor wafer
(being typically silicon nitride) to allow to be in direct contact aspect between conductive trace and semiconductor, frit is also important.Frit
It is generally also important in terms of forming Ohmic contact with semiconductor emission body.
Contact quality between conductive trace and semiconductor wafer aids in determining whether the efficiency of final solar cell.Most
Good frit needs to optimize to flow at correct temperature, and provides the correct etching degree of anti-reflecting layer.Provided that
Etching it is very little, then the contact between semiconductor wafer and conductive trace will be insufficient, leads to high contact resistance.On the contrary, mistake
The etching of degree may cause to deposit the islands great Yin in the semiconductors, destroy its pn-junction, and electricity is converted the solar into reduce it
The ability of energy.
Nearest attention has been concentrated on the frit material improved and be included in the electroconductive paste for photovoltaic cell, with
Good performance balance is provided.
Including being all dispersed in the conductive powder in organic media, frit and sometimes one or more other additives
Electroconductive paste be also used for forming conductive trace or conductive coating, the thin-film solar cells in thin-film solar cells and pass through
It will manufacture on the substrate of one or more photovoltaic material veneers to such as glass or metal, it is described comprising being all dispersed in
The electroconductive paste of conductive powder, frit and sometimes one or more other additives in organic media be also used for it is a series of its
In his electronic application, including passive electrical components, such as the terminal electrode of zinc oxide varistor component, (more for MLCC
Layer ceramic capacitor) terminal, coating TCO (transparent conductive oxide) glass substrate on electrode, NTC (negative temperature coefficient)
The metallization of conductive layer, function piezoelectric ceramics on thermistor；And automobile application, including rear window, side window, heatable mirror
Son and windshield and antenna.
Invention content
Remain a need for good performance balance, for example for the electroconductive paste of solar cell.Particularly, it still needs
It is used for the electroconductive paste of solar cell, provides excellent (reduction) contact resistance without negatively affecting solar-electricity
The pn-junction in pond, and it includes frit or flows at a suitable temperature conductive to be fired during the manufacture of solar cell
The other materials of paste.
, it is surprising that it has been found by the present inventors that the particle for the basic crystalline state being included in electroconductive paste can obtain
Good with as the result that the paste including glass is obtained or better result.Particularly, the inventors have discovered that including two
The inorganic particle mixture of kind or more the particle of the basic crystalline state of different metal compound is suitble to replace frit.
Therefore, in the first preferred aspect, the present invention is provided to form the electroconductive paste of conductive trace or coating on substrate,
The paste includes the solid portion being dispersed in organic media, and the solid portion includes that conductive material and inorganic particle mix
Object, wherein the inorganic particle mixture includes the particle and base of the basic crystalline state of two or more different metal compounds
This is free of lead；And the glass content of the wherein described solid portion is less than 1 weight %.For example, the electroconductive paste can be used for the sun
It can battery.
Using the basic crystalline state of different metallic compounds particle be particularly advantageous in that it from manufacture electroconductive paste mistake
Glass forming step is eliminated in journey.Glass forming step usually has high energy demand, because it needs to add glass precursor
Temperature of the heat to the fusing point higher than the crystalline material for manufacturing glass.Due to glass relatively low softening point and fusing point, so
Usually by glass in electroconductive paste.In general, the glass used in electroconductive paste flows at a temperature in the range of about 400-700 DEG C
It is dynamic.Present inventors have surprisingly discovered that although being used for the metallization of the basic crystalline state of at least some of paste of the present invention
Closing object has significantly higher fusing point, but these mixtures still show flowing similar with frit and melting behavior, this makes
Obtaining them can use in the case of the firing curve and manufacturing method similar with the paste comprising frit.
As it will appreciated by a person of ordinary skill, avoiding the glass forming step of energy-intensive for solar cell
Electroconductive paste has the advantage that except field.Inventors believe that their invention be also applied in other electronic applications (such as this
Text those of refers to) it is used to form the electroconductive paste of conductive trace and conductive coating.
The present inventor has also been discovered that certain particle size distribution can have advantageous effect.Especially they have been
Observe that paste and the behavior of the electrode of firing tend to improve with the reduction of particle size.
Therefore, in the second preferred aspect, the present invention is provided to form the electroconductive paste of conductive trace or coating on substrate,
The paste includes the solid portion being dispersed in organic media,
The solid portion includes conductive material and inorganic particle mixture；
The wherein described inorganic particle mixture includes with two or more the particle size being applicable in the following conditions
The particle of the basic crystalline state of distribution:
(a)D10≤0.41μm；
(b)D50≤1.6μm；
(c)D90≤4.1μm；
(d)(D50–D10)≤1.15μm；
(e)(D90–D50)≤2.5μm；
(f)(D90–D10)≤3.7μm；With
(g)(D50/D10)≤3.85。
For example, the electroconductive paste can be used for solar cell.
In a further preferred aspect, the present invention provides the method for preparing electroconductive paste as described herein, and it includes to appoint
What sequence mixes the component and organic media, conductive material of inorganic particle mixture.The method may be embodied in inorganic particulate
The particle of the basic crystalline state of grain mixture is co-mulled and made into the inorganic particle mixture before being mixed with organic media and conductive material
Basic crystalline state particle.
In a further preferred aspect, the method that this hair provides the surface electrode for manufacturing solar cell, the side
Method includes electroconductive paste as described herein to be applied to semiconductor substrate, and fire applied electroconductive paste.The present invention also provides
Method for manufacturing conductive trace or coating on substrate, the method include that electroconductive paste as described herein is applied to lining
Bottom, and fire applied electroconductive paste.
In a further preferred aspect, the present invention is provided to the electrode of solar cell, the electrode includes semiconductor
Conductive trace on substrate, wherein the conductive trace by fire on a semiconductor substrate as described herein paste by obtain or
It can get.The present invention also provides the solar cells comprising surface electrode.The present invention also provides comprising with shape on the surface thereof
At conductive trace or coating substrate electronic unit, wherein the conductive trace or coating are by firing on substrate such as this
Paste described in text and obtain or can get.
In a further preferred aspect, the present invention provides electroconductive paste as described herein on the surface of manufacture solar cell
Purposes in electrode.The present invention also provides electroconductive paste as described herein in manufacture comprising with the conduction formed on the surface thereof
Purposes in the electronic section of the substrate of trace or coating.
The invention further relates to inorganic blends (inorganic particle mixture) itself as described herein.
Description of the drawings
Fig. 1 shows the exemplary firing curve for solar cell prepared in embodiment.
Fig. 2 shows the XRD analysis of inorganic particle mixture.
Fig. 3 shows the XRD analysis for the inorganic particle mixture being co-mulled and made into.
Fig. 4 shows the inorganic particle mixing formed by grinding the component of each component and subsequent mixed grinding respectively
The XRD analysis of object.
Fig. 5 shows the comparison of the sintering curre of various inorganic particle mixtures and glass.
Fig. 6 shows the comparison of the sintering curre of various other inorganic particle mixtures.
Specific implementation mode
The preferred and/or optional feature of the present invention will be illustrated now.Unless the context otherwise requires, otherwise of the invention
Any aspect can with the present invention any other aspect combine.Unless the context otherwise requires, otherwise any aspect appoint
What preferred and/or optional feature can alone or in combination be combined with any aspect of the present invention.
For example, the discussion of inorganic particle mixture content, raw material and particle size distribution be equally applicable to be related to paste,
The aspect of method and the present invention of blend.
The electroconductive paste of the present invention includes organic media and solid portion.Solid portion includes that conductive material and inorganic particle are mixed
Close object.By discuss in these each and using they manufacture electroconductive pastes various methods.
Inorganic (such as oxide) granulate mixture-content
The solid portion of electroconductive paste as described herein contains the blend of the inorganic material of the basic crystalline state of granular form.
This inorganic blend herein is sometimes referred to as oxide particle mixture.Oxide as described below, carbonate, nitrate
Or other materials can mix (such as by being co-mulled and made into), then be introduced into electroconductive paste.
In general, in some aspects of the invention, inorganic particle mixture is by two or more different particulate inorganics
Material, as metallic compound (such as metal oxide, metal carbonate or metal nitrate) forms.Particle is substantially crystalline state
's.The mixture can be containing non-oxidic material and can be by not being that the material of oxide is formed.
Granular property means that there are the discrete of each inorganic component, separation or individual particles.These with previously
The fusion for the frit known, amorphous phase structure is different.Since inorganic particle is substantially crystalline state, they do not show glass
Glass transition.
In solid portion, there are conductive materials and inorganic particle mixture.It is possible that these for solid portion only
One component.Therefore solid portion can be only made of conductive material and inorganic particle mixture.
Therefore, in solid portion, the content of amorphous phase oxide material or glass is relatively low.The glass of solid portion contains
Amount can be less than 1 weight %.For example, the total weight relative to solid portion, the glass content of solid portion can be less than 0.5 weight
% is measured, 0.25 weight % is less than, is less than 0.1 weight %, be less than 0.05 weight % or is less than 0.01 weight %.Solid portion can be with
It is substantially free of glass.In some embodiments, solid portion does not include any glass intentionally added and/or any intentional shape
At glass phase.
It will be understood to those of skill in the art that glass material and amorphous material or the amorphous areas even in crystalline material
Domain is simultaneously non-synonymous.Glass transition is presented in glass material.Although glass may include that (they can be incomplete for some crystalline domains
It is amorphous), but these are different from discrete crystalline particles as described herein.
Certainly, it would be recognized by those skilled in the art that due to used processing conditions property, even if basic when using
When the raw material of crystalline state, some amorphous phases or glass phase can be also formed.In aspects of the present invention, this is minimized.For example, can
Can exist the reaction of the surface of some oxide particles, by grind, or the raw material from such as lithium carbonate decomposition carbon
It deposits and causes.
However, the difference with known materials can be characterized by lacking glass transition (not showing Glass Transition).
Inorganic (such as oxide) granulate mixture may include metal oxide.Reader will be apparent that many such oxidations
Object is known.Inorganic particle mixture includes the particle of basic crystalline state, is typically of the basic crystalline state of metallic compound
Grain.Each metallic compound can be for example selected from metal oxide, metal carbonate or metal nitrate.Particularly, it carefully examines
The compound (such as oxide) of usually used type in the electroconductive paste manufacturing field for solar cell is considered.
May include some special metal chemical combination objects in the present invention include TeO2、Li2O、Li2CO3、Bi2O3、Bi5
(OH)9(NO3)4、ZnO、Ce2O3、CeO2、Na2O、Na2CO3And MoO3。
For example, in some embodiments, inorganic particle mixture of the invention include tellurium compound such as tellurium oxide,
Align tellurite or TeO2Basic crystalline state particle.In some embodiments, inorganic particle mixture of the invention includes
The compound of cerium such as cerium oxide or CeO2Basic crystalline state particle.In some embodiments, it is of the invention it is inorganic (such as
Oxide) granulate mixture include bismuth compound such as bismuth nitrate or bismuth oxide, bismuth oxide or Bi2O3Basic crystalline state
Particle.
Inorganic particle mixture may include two or more different metallic compounds, be in some embodiments
Three or more, four kinds or more, the different metallic compound of five kinds or more or six kinds or more.
The content of contained different metallic compounds is it is of course possible to difference.There may be it is a kind of, two kinds, it is three kinds or more
Kind metallic compound, has the content for being apparently higher than other contained metallic compounds.For example, in some embodiments,
Compound (such as the TeO of tellurium2) content be higher than any other metallic compound content.In some embodiments, tellurium
Compound and the compound of bismuth are the one kind having in two kinds of compounds-i.e. compound of tellurium and the compound of bismuth of highest content
It is the compound with highest content, another kind is with time compound of highest content.Content used herein can refer to weight
The content of amount.
In certain embodiments, one or more (such as each) metallic compounds only include a type of gold substantially
Belong to element.That is, there are metals and other nonmetallic (such as oxygen) atoms or ion in the compound.That is,
It can there is only single cationic substances substantially in the given metallic compound being included in the invention.For example, can make
With XRD the only presence of the metallic atom or ion of single type substantially is identified, to confirm the basic crystalline state of metallic compound
The crystal structure of particle corresponds to the crystal structure of single metallic compound (such as oxide).As those skilled in the art will manage
Solution, single metallic compound may include can be different metal atom or ion incidental impurities.This incidental impurities will be with
Extremely low level (such as relative to the entire metallic compound discussed<1 mole of % or<0.5 mole of %) it is present in metal
In compound.In addition, the processing (such as being co-mulled and made into) of metallic compound can cause some surfaces of compound modified or reaction.
However, in this case, most of (bulk) material keeps the metallic compound of single metal, and still can institute as above
It states and is identified by XRD.
Two or more metallic compounds, it is in some embodiments, three or more, four kinds or more, five
Kind or more or six kinds or more metallic compounds only include a type of metallic element substantially.
Therefore, in some embodiments, it is included in each compound in inorganic particle mixture or other materials only
Including a type of metallic element.Therefore it is possible that inorganic particle mixture is substantially free of the metallic compound of mixing, example
Such as mixed oxide.Mixed oxide includes the metallic element of more than one type.
As used herein, term " oxide for being substantially free of mixing " is intended to include the mixed oxide without intentionally adding
Inorganic (such as oxide) granulate mixture.For example, inorganic (such as oxide) granulate mixture may include being less than 0.1 weight
The oxide for measuring the mixing of %, is, for example, less than 0.05 weight %, is less than 0.01 weight % or the mixing less than 0.005 weight %
Oxide.For example, inorganic particle mixture can not include the oxide of the mixing intentionally added.As used herein, term " base
This is free of mixed metallic compound " it should similarly explain.
Mixed oxide is well known in the art.In the frit formation technology of the prior art, it is usually formed
Mixed oxide.Present inventors have surprisingly discovered that (such as by blending or being co-mulled and made into) can alternatively be prepared
Be used to manufacture in the prior art this glass oxide and other starting materials to obtain basic crystalline state, the nothing of granular form
Machine (such as oxide) granulate mixture, and obtain identical or better result.
Inorganic compound content as described herein is provided with weight percent, unless specified otherwise herein.These weight percent
It is the total weight relative to inorganic particle mixture.Unless specified otherwise herein, otherwise weight percent is in inorganic particle mixture
Or it is used as the percentage of the component of starting material in the preparation of electroconductive paste, on the basis of oxide.
Inorganic particle mixture described herein is generally free from limitation.The many of electroconductive paste suitable for solar cell
Different oxides are well known in the present art.
It may be preferred that inorganic particle mixture is substantially free of lead.As used herein, term " being substantially free of lead " is intended to
It include the inorganic particle mixture without the lead intentionally added.For example, inorganic particle mixture may include being less than 0.1 weight %
PbO, be, for example, less than 0.05 weight %, be less than the 0.01 weight % or PbO less than 0.005 weight %.
It may be preferred that inorganic particle mixture is substantially free of boron.As used herein, term " being substantially free of boron " is intended to
It include the inorganic particle mixture without the boron intentionally added.For example, inorganic particle mixture may include being less than 0.1 weight %
Boron (with B2O3Calculate), it is, for example, less than 0.05 weight %, is less than 0.01 weight % or less than 0.005 weight % (with B2O3Meter
It calculates).
In some embodiments, inorganic particle mixture includes the compound of tellurium, such as TeO2.Inorganic particle mixture
May include at least 20 weight %, at least 25 weight %, at least 30 weight %, at least 35 weight %, at least 40 weight % or extremely
The compound of the tellurium of few 45 weight % is (with TeO2It calculates).Inorganic particle mixture may include 80 weight % or less, 75 weights
% or less is measured, 70 weight % or less, 65 weight % or less or 60 weight % or less telluriums compound are (with TeO2
It calculates).For example, inorganic (such as oxide) granulate mixture may include the compound of the tellurium of 35 to 65 weight % (with TeO2
It calculates).
In some embodiments, inorganic particle mixture includes the compound of bismuth, such as Bi2O3.Inorganic particle mixture
May include at least 10 weight %, at least 15 weight %, at least 18 weight %, the bismuth of at least 20 weight % or at least 25 weight %
Compound (with Bi2O3It calculates).Inorganic particle mixture may include 60 weight % or less, 55 weight % or less, 50 weights
% or less or 45 weight % or less bismuths compounds are measured (with Bi2O3It calculates).For example, inorganic particle mixture can be with
The compound of bismuth including 20 to 50 weight % is (with Bi2O3It calculates).
Alternatively, the compound of bismuth can be bismuth nitrate, such as Bi5O(OH)9(NO3)4.Nitrate (such as the Bi of bismuth5O
(OH)9(NO3)4) can be at least 10 weight %, at least 15 weight %, at least 18 weight %, at least 20 weight % or at least 25
The amount of weight % uses.It can be with 60 weight % or less, 55 weight % or less, 50 weight % or less or 45 weights
% or less amounts are measured to use.Such as it can be used with the amount of 20 to 50 weight %.It in some embodiments, can be preferred
Use Bi2O3。
In some embodiments, inorganic particle mixture includes compound (such as the CeO of cerium2).Inorganic particle mixes
Object can include 0 weight % or more, for example, at least 0.1 weight %, at least 0.2 weight %, at least 0.5 weight %, at least 1
Weight %, at least 1.5 weight %, at least 2 weight %, at least 2.5 weight %, at least 3 weight %, at least 3.5 weight %, at least
4 weight %, at least 4.5 weight %, at least 5 weight %, the compound of at least 6 weight % or at least cerium of 7 weight % is (with CeO2
It calculates).Inorganic particle mixture can include 22 weight % or less, 20 weight % or less, 17 weight % or less, 15 weights
Measure % or less, 14 weight % or less, 13 weight % or less, 12 weight % or less, 11 weight % or less, 10 weights
% or less or 5 weight % or less ceriums compounds are measured (with CeO2It calculates).Specially suitable CeO2Content is 1 weight
Measure % to 15 weight %.
Inorganic (such as oxide) granulate mixture may include compound (such as the SiO of silicon2).For example, inorganic particle
Mixture may include 0 weight % or more, 0.1 weight % or more, 0.5 weight % or more or 1 weight % or more,
The compound of the silicon of 2 weight % or more or 2.5 weight % or more is (with SiO2It calculates).Inorganic (such as oxide) particle
Mixture may include 20 weight % or less, 15 weight % or less, 10 weight % or less, 7 weight % or less or 5
The compound of weight % or less silicon is (with SiO2It calculates).For example, inorganic particle mixture may include 0.1 to 7 weight %
SiO2。
In some embodiments, it may be preferred that inorganic particle mixture is substantially free of silicon.As used herein, art
Language " being substantially free of silicon " is intended to include the inorganic particle mixture without the silicon intentionally added.For example, inorganic (such as oxide)
Granulate mixture may include being less than the silicon of 0.1 weight % (with SiO2Calculate), it is, for example, less than 0.05 weight %, is less than 0.01 weight
% or silicon less than 0.005 weight % are measured (with SiO2It calculates).
Inorganic (such as oxide) granulate mixture may include alkali metal compound, such as selected from lithium, sodium, potassium and rubidium
It is one or more in compound, it is preferably selected from one or more in the compound of lithium, sodium and potassium, the change of more preferable lithium and sodium
Close the one or both of object.One or more (such as each) alkali metal compounds can be easily alkali carbonate.
In some embodiments, preferably inorganic (such as oxide) granulate mixture includes the compound of lithium, such as lithium carbonate.
Inorganic particle mixture may include 0 weight % or more, 0.1 weight % or more, 0.5 weight % or more or
The alkali metal compound of 1 weight % of person or more is calculated based on oxide.Inorganic particle mixture may include 10 weight % or
Less, 8 weight % or less, 7 weight % or less, 5 weight % or less, 4 weight % or less alkali metal compounds, base
It is calculated in oxide.
Inorganic (such as oxide) granulate mixture may include 0 weight % or more, 1 weight % or more, 2 weight %
Or more, the compound of the lithium of 4 weight % or more, 5 weight % or more or 6 weight % or more, by Li2O is calculated.Nothing
Machine (such as oxide) granulate mixture may include 20 weight % or less, 15 weight % or less, 13 weight % or less, 6
Weight % or less, 10 weight % or less or 8 weight % or less lithiums compound, by Li2O is calculated.For example, nothing
Machine (such as oxide) granulate mixture may include the compound of the lithium of 5 to 12.5 weight %, with Li2O is calculated.
Note that can be used for prepare include lithium the inorganic particle mixture of compound and a kind of specified raw material of electroconductive paste be
Li2CO3.It can be with 0 weight % or more, 1 weight % or more, 2 weight % or more, 4 weight % or more, 5 weight %
Or more or the amount of 6 weight % or more be used as raw material.It can be with 20 weight % or less, 15 weight % or less, 13
Weight % or less, 6 weight % or less, 10 weight % or less or 8 weight % or less amounts are used as raw material.For example,
It can be used as raw material with the amount of 5 to 12.5 weight %.
In some embodiments, inorganic particle mixture includes both the compound of tellurium and the compound of lithium.For example, can
To contain both tellurium oxide and lithia.In aspects of the present invention, the ratio of the compound of these lithiums and tellurium can also be controlled
System.For example, molar ratio (the Te of Te and Li:Li ratios) it can be 1:1 to 100:In the range of 1.Te:Li ratios can be at least
2:1, at least 3:1, at least 4:1, at least 5:1 or at least 6:1.Te:Li ratios can be 100:1 or smaller, 50:1 or smaller,
25:1 or smaller, 20:1 or smaller, 15:1 or smaller, 10:1 or smaller, 8:1 or smaller, 7.5:1 or smaller or 7:1 or more
It is small.For example, molar ratio (the Te of Te and Li:Li ratios) it can be 3:1 to 10:In the range of 1, such as 5:1 to 8:1 range
It is interior.
Inorganic (such as oxide) granulate mixture may include the compound (such as ZnO) of zinc.For example, inorganic particle is mixed
It may include 0 weight % or more, 0.1 weight % or more, 0.5 weight % or more to close object, 1 weight % or more or
The compound (being calculated with ZnO) of the zinc of 1.5 weight % or more.Inorganic particle mixture may include 15 weight % or less,
10 weight % or less, 7 weight % or less or 5 weight % or less zinc compound (being calculated with ZnO).For example, nothing
Machine (such as oxide) granulate mixture may include the compound of the zinc of 0.5 to 7 weight %, be calculated with ZnO.
In some embodiments, it may be preferred that inorganic (such as oxide) granulate mixture is substantially free of zinc.Such as
Used herein, term " being substantially free of zinc " is intended to include the inorganic particle mixture without the zinc intentionally added.For example, inorganic particulate
Grain mixture may include the zinc (being calculated with ZnO) less than 0.1 weight %, be, for example, less than 0.05 weight %, be less than 0.01 weight
Measure % or the zinc (being calculated with ZnO) less than 0.005 weight %.
Inorganic particle mixture may include compound (such as the MoO of molybdenum3).For example, inorganic particle mixture can wrap
0 weight % or more, 0.1 weight % or more are included, the compound of the molybdenum of 0.5 weight % or more is (with MoO3It calculates).It is inorganic
Granulate mixture may include 10 weight % or less, 5 weight % or less or 3 weight % or less molybdenums compounds
(with MoO3It calculates).For example, inorganic (such as oxide) granulate mixture may include the molybdenum of 0.1 to 5 weight % (with MoO3Meter
It calculates).
In some embodiments, it may be preferred that inorganic particle mixture is substantially free of molybdenum.As used herein, art
Language " being substantially free of molybdenum " is intended to include the inorganic particle mixture without the molybdenum intentionally added.For example, inorganic particle mixture can
To include being less than the molybdenum of 0.1 weight % (with MoO3Calculate), it is, for example, less than 0.05 weight %, less than 0.01 weight % or is less than
The molybdenum of 0.005 weight % is (with MoO3It calculates).
Inorganic particle mixture may include compound (such as the Cr of chromium2O3).For example, inorganic particle mixture can wrap
0 weight % or more, 0.1 weight % or more are included, the compound of the chromium of 0.5 weight % or more is (with Cr2O3It calculates).It is inorganic
(such as oxide) granulate mixture may include 10 weight % or less, 5 weight % or less or 3 weight % or less
Chromium (with Cr2O3It calculates).For example, inorganic (such as oxide) granulate mixture may include 0.1 to 5 weight % chromium (with
Cr2O3It calculates).
In some embodiments, it may be preferred that inorganic particle mixture is substantially free of chromium.As used herein, art
Language " being substantially free of chromium " is intended to include the inorganic particle mixture without the chromium intentionally added.For example, inorganic particle mixture can
To include being less than the chromium of 0.1 weight % (with Cr2O3Calculate), it is, for example, less than 0.05 weight %, less than 0.01 weight % or is less than
The chromium of 0.005 weight % is (with Cr2O3It calculates).
Inorganic particle mixture may include compound (such as the WO of tungsten3).For example, inorganic particle mixture may include
0 weight % or more, 0.1 weight % or more, the compound of the tungsten of 0.5 weight % or more is (with WO3It calculates).Inorganic particle
Mixture may include 10 weight % or less, 5 weight % or less or 3 weight % or less tungsten compounds (with
WO3It calculates).For example, inorganic (such as oxide) granulate mixture may include the compound of the tungsten of 0.1 to 5 weight % (with WO3
It calculates).
In some embodiments, it may be preferred that inorganic particle mixture is substantially free of tungsten.As used herein, art
Language " being substantially free of tungsten " is intended to include the inorganic particle mixture without the tungsten intentionally added.For example, inorganic particle mixture can
Include the tungsten less than 0.1 weight % (with WO3In the presence of), it is, for example, less than 0.05 weight %, is less than 0.01 weight % or less than 0.005
The tungsten of weight % is (with WO3It calculates).
Inorganic particle mixture may include the compound (such as BaO) of barium.For example, inorganic particle mixture may include
0 weight % or more, 0.1 weight % or more, the compound (being calculated with BaO) of the barium of 0.5 weight % or more.Inorganic particle
Mixture may include 10 weight % or less, 5 weight % or less or 3 weight % or less barium compounds (with
BaO is calculated).For example, inorganic particle mixture may include the compound (being calculated with BaO) of the barium of 0.1-5 weight %.
Inorganic particle mixture may include compound (such as the P of phosphorus2O5).For example, inorganic particle mixture may include
The phosphorus of 0 weight % or more, 0.1 weight % or more, 0.5 weight % or more or 1 weight % or more compound (with
P2O5It calculates).Inorganic particle mixture may include 10 weight % or less, 7 weight % or less, 5 weight % or less or
The compound of 3 weight % or less phosphorus is (with P2O5It calculates).
Inorganic particle mixture may include other components, such as other oxide components.Normally, inorganic particle mixes
Object, which will will include, amounts to 20 weight % or less, 10 weight % or less, 7 weight % or less, 5 weight % or less, 3 weights
Measure % or less, 2 weight % or less or 1 weight % or less other components.Inorganic particle mixture may include to
The other components of few 0.1 weight %.Other components can be compound (such as the GeO selected from germanium, calcium, zirconium, copper, silver and aluminium2、
CaO、ZrO2, CuO, AgO and Al2O3) in it is one or more.
The selection of the ingredient of inorganic particle mixture or blend when can be by firing desired flow behavior instruct.This
Inventor has found that certain mixtures are especially suitable.For example, inorganic particle mixture can preferably comprise provide tellurium source (such as
TeO2) and alkali metal (preferably lithium) source (such as LiCO3Or Li2O the mixture of ingredient).Can also include bismuth source (for example,
Bi2O3Or Bi5O(OH)9(NO3)4).Can also include zinc source (for example, ZnO).Content can be as described above.
Inorganic particle mixture can be made of composition as described herein and subsidiary impurity substantially.In such case
Under, it is that the total weight % of the component will be 100 weight %, and any surplus is as the skilled person will readily understand
Subsidiary impurity.Normally, any subsidiary impurity will be with 0.1 weight % or less, 0.05 weight % or less, 0.01 weight
% or less is measured, 0.05 weight % or less, 0.001 weight % or less or 0.0001 weight % or less amounts exist.
The solid portion of the electroconductive paste of the present invention may include the inorganic particle mixture of 0.1 to 15 weight %.Electroconductive paste
Solid portion may include at least 0.5 weight % or at least 1 weight % inorganic particle mixture.The solid portion of electroconductive paste
May include 10 weight % or less, 7 weight % or less or 5 weight % or less inorganic particle mixtures.
It may be preferred that inorganic particle mixture includes at least the compound of lithium and tellurium.It may be preferred that inorganic particulate
Grain mixture includes at least the compound of lithium, tellurium and bismuth.It may be preferred that inorganic particle mixture include at least lithium, tellurium and
The compound of zinc.It may be preferred that inorganic particle mixture includes at least the compound of lithium, tellurium, zinc and bismuth.It can be preferred
It is that inorganic particle mixture includes at least lithium, tellurium, sodium, the compound of bismuth and zinc.It may be preferred that inorganic particle mixture
Including at least the compound of lithium, tellurium and cerium.It may be preferred that inorganic particle mixture includes at least the change of lithium, tellurium, cerium and bismuth
Close object.It may be preferred that inorganic particle mixture includes at least the compound of lithium, tellurium, cerium and zinc.It may be preferred that nothing
Machine granulate mixture includes at least the compound of lithium, tellurium, zinc, cerium and bismuth.It may be preferred that inorganic particle mixture at least wraps
Compound containing lithium, tellurium, sodium, bismuth, cerium and zinc.
Inorganic particle mixture-particle size
In some embodiments of the present invention, the particle size of inorganic particle mixture can be not particularly limited.
However, inventor has found that the inorganic particle mixture being distributed with particular particle size surprisingly has
With.Therefore, the control of particle size distribution is important in some aspects of the invention.
The present invention can be related to the embodiment that wherein inorganic particle mixture has following any particle size distribution：
(a)D10≤0.41μm；
(b)D50≤1.6μm；
(c)D90≤4.1μm；
(d)(D50–D10)≤1.15μm；
(e)(D90–D50)≤2.5μm；
(f)(D90–D10)≤3.7μm；Or
(g)(D50/D10)≤3.85。
Can meet in the present invention it is one or more in these requirements, two or more, three or more, four or
More, five or more or six or more.
In some embodiments, (a) is met the requirements.In some embodiments, (b) is met the requirements.In some implementations
In scheme, meet the requirements (c).In some embodiments, (d) is met the requirements.In some embodiments, (e) is met the requirements.
In some embodiments, (f) is met the requirements.In some embodiments, (g) is met the requirements.
In embodiments of the invention, any combinations of these requirements can be met.
About requiring (a), D10It it is 0.41 μm or lower, such as 0.4 μm or lower, 0.39 μm or lower, 0.35 μm or more
It is low, 0.32 μm or lower, 0.3 μm or lower, 0.28 μm or lower, 0.25 μm or lower or 0.24 μm or lower.
D10Value be preferably 0.4 μm or lower.
Normally, D10Particle size can be at least 0.1 μm, at least 0.12 μm, at least 0.14 μm, at least 0.17 μm or extremely
It is 0.2 μm few.
Therefore, in some embodiments, D10In 0.2 μm≤D10In the range of≤0.4 μm.
About requiring (b), the D of inorganic particle mixture50Preferably lower than or equal to 1.6 μm.D50It can be 1.55 μm or more
It is low, 1.5 μm or lower, 1.45 μm or lower, 1.4 μm or lower, 1.35 μm or lower, 1.3 μm or lower, 1.25 μm or more
It is low, 1.2 μm or lower, 1.15 μm or lower, 1.1 μm or lower, 1.05 μm or lower, 1 μm or lower or 0.95 μm or more
It is low.
D50Value be preferably 1.05 μm or lower.
In general, D50Particle size can be at least 0.1 μm, at least 0.3 μm, at least 0.5 μm or at least 0.8 μm.
Therefore, in some embodiments, D50In 0.3 μm≤D50In the range of≤1.05 μm.
About requiring (c), the D of inorganic particle mixture90Preferably lower than or equal to 4.1 μm.D90Can be 4 μm or lower,
3.8 μm or lower, 3.6 μm or lower, 3.4 μm or lower, 3.2 μm or lower, 3 μm or lower, 2.8 μm or lower, 2.6 μm or
It is lower, 2.4 μm or lower, 2.2 μm or lower, 2.1 μm or lower, 2 μm or lower or 1.9 μm or lower.
D90Value be preferably 2.2 μm or lower.
Normally, D90Particle size can be at least 1 μm, at least 1.2 μm, at least 1.4 μm or at least 1.5 μm.
Therefore, in some embodiments, D90In 1.4 μm≤D90In the range of≤2.2 μm.
About requiring (d), (D50-D10) be 1.15 μm or lower, such as 1.1 μm or lower, 1 μm or lower, 0.8 μm or
It is lower, 0.6 μm or lower, 0.59 μm or lower, 0.58 μm or lower, 0.57 μm or lower, 0.56 μm or lower, 0.55 μm or
It is lower, 0.54 μm or lower or 0.53 μm or lower.
(D50-D10) value be preferably 0.6 μm or lower.
Normally, D50With D10Between difference can be at least 0.1 μm, at least 0.2 μm, at least 0.3 μm or at least 0.35 μ
m。
Therefore, in some embodiments, (D50-D10) in 0.3 μm≤(D50-D10In the range of)≤0.6 μm.
About requiring (e), (D90-D50) be 2.5 μm or lower, such as 2 μm or lower, 1.75 μm or lower, 1.5 μm or
It is lower, 1.25 μm or lower, 1.15 μm or lower, 1.1 μm or lower, 1.05 μm or lower, 1 μm or lower or 0.95 μm or
It is lower.
(D90-D50) value be preferably 1.15 μm or lower.
Normally, D90With D50Between difference can be at least 0.5 μm, at least 0.6 μm, at least 0.7 μm or at least 0.75 μ
m。
Therefore, in some embodiments, (D90-D50) in 0.6 μm≤(D90-D50In the range of)≤1.15 μm.
About requiring (f), (D90-D10), i.e. D90With D10Difference, preferably lower than or equal to 3.7 μm.(D90-D10) value can
To be 3.5 μm or lower, 3 μm or lower, 2.5 μm or lower, 2 μm or lower, 1.8 μm or lower, 1.6 μm or lower, 1.5 μm
Or it is lower, 1.45 μm or lower, 1.4 μm or lower or 1.35 μm or lower.
(D90-D10) value be preferably 1.8 μm or lower.
In general, D90With D10Between difference can be at least 1 μm, at least 1.1 μm, at least 1.2 μm or at least 1.3 μm.
Therefore, (D in some embodiments90-D10) in 1.1 μm≤(D90-D10In the range of)≤1.8 μm.
About requiring (g), (D50/D10), i.e. D50Divided by D10Obtained value is less than or equal to 3.85.(D50/D10) value
Can be 3.8 or lower, 3.7 or lower, 3.6 or lower, 3.5 or lower, 3.4 or lower, 3.3 or lower, 3.2 or lower,
3.1 or lower, 3 or lower, 2.8 or lower or 2.6 or lower.
(D50/D10) value be preferably 3.6 or lower.
Normally, D50With D10Between ratio can be at least 1, at least 1.5, at least 2 or at least 2.3 μm.
Therefore, (D in some embodiments50/D10) in 2.2≤(D50/D10In the range of)≤3.6.
Particle size as described herein and distribution can use laser diffractometry (such as to use Malvern
Mastersizer 2000) it measures.
Inorganic particle mixture-preparation
Inorganic particle mixture can be prepared by the raw material of metallic compound needed for mixing.On these raw materials can be
Oxide, the carbonate etc. that face discusses.Mixing can carry out in known manner.In general, not carrying out inorganic particle mixture
Melting, quenching or other glass production technologies.
Mixing or blending above-mentioned material can generate and be suitable for the invention inorganic particle mixture.These raw materials can be with
The form of basic crystalline state uses.
Mixing or Mixing Technology are well-known in the art.The inventors have discovered that co-rotational procedure exists
It is especially effective to prepare suitable inorganic (such as oxide) granulate mixture aspect.It is not wishing to be bound by theory, it is believed that this attribution
In it to reducing particle size and/or providing the effect of narrow particle size distribution.Alternatively, each group of inorganic particle mixture
Point can before being combined respectively grinding (or if necessary, otherwise process with provide needed for particle ruler
Very little and/or particle size distribution), to provide inorganic particle mixture.
The raw material for mixing (such as being co-mulled and made into) inorganic particle mixture can be later by gained blend and organic media
It is for example blended in any order with conductive material.Being co-mulled and made into can add to the unique of raw material progress of inorganic particle mixture
Work.For example, the method that glass production can not be carried out.It is understood that can by inorganic particle mixture each
Component is respectively added in conductive material and organic media to obtain the electroconductive paste of the present invention.
For example, oxide discussed above, carbonate, nitrate etc. can be blended.Then it can grind or not grind institute
Obtain mixture.Upon grinding, which can carry out for example in planetary mill to provide required as discussed above
Particle size is distributed.Wet lapping can carry out in organic solvent such as butyldiglycol.Then the powder that gained can be blended
It is dry.It may be screened, further to adjust particle size distribution.
Electroconductive paste
Electroconductive paste is suitable for forming conductive trace or coating on substrate.It is particularly suitable for for example in solar cell
In, surface electrode is formed on a semiconductor substrate.Electroconductive paste is also suitable for forming electrode in thin-film solar cells.Electroconductive paste
It can be positive side electroconductive paste.
The solid portion of the electroconductive paste of the present invention may include the conductive material of 80 to 99.9 weight %.For example, solid part
Point may include at least 80 weight %, at least 82 weight %, at least 85 weight %, at least 87 weight %, at least 90 weight %, until
The conductive material of few 93 weight % or at least 95 weight %.Solid portion may include 99.9 weight % or less, 99.5 weights
Measure % or less, 99 weight % or less, 95 weight % or less, 92 weight % or less, 90 weight % or less, 88 weights
Measure % or less or 86 weight % or less conductive materials.
In general, conductive material can be the key component of solid portion, i.e. the highest ingredient of content of solid portion.
Conductive material can include one or more metals in silver, copper, nickel and aluminium.Preferably, conductive material packet
Argentiferous is made of silver.This is in solar cell application, such as is pasting the feelings to be contacted with the N-shaped emitter of solar cell
It is particularly preferred under condition.In some embodiments, the feelings that especially contacted with the p-type emitter of solar cell in paste
Under condition, conductive material can include aluminium, such as it can be the blend of silver and aluminium.
Conductive material can be provided with particle, such as the form of metallic particles.The form of particle is not particularly limited, but can
In the form of being or mixtures thereof sheet body, spheric granules, granule, crystal, powder or other irregular particles.
The particle size of conductive material is not particularly limited in the present invention.In general, D50Particle size can be at least 0.1
μm, at least 0.5 μm or at least 1 μm.D50Particle size can be 15 μm or smaller, 10 μm or smaller, 5 μm or smaller, 4 μm or more
It is small, 3 μm or smaller or 2 μm or smaller.Particle size can use laser diffractometry (such as to use Malvern
Mastersizer 2000) it measures.
The solid portion of the electroconductive paste of the present invention may include that inorganic (such as oxide) particle of 0.1 to 15 weight % is mixed
Close object.For example, solid portion may include at least 0.2 weight %, at least 0.5 weight % or at least weight % it is inorganic (such as
Oxide) granulate mixture.Solid portion may include 10 weight % or less, 7 weight % or less or 5 weight % or more
Few inorganic (such as oxide) granulate mixture.
The surface area of conductive material is not particularly limited in the present invention.For example, it can be at least 0.1m2/ g, at least
0.2m2/ g, at least 0.3m2/ g, at least 0.4m2/ g or at least 0.5m2/g.For example, it can be 5m2/ g or smaller, 3m2/ g or more
It is small, 2m2/ g or smaller, 1m2/ g or smaller, 0.8m2/ g or smaller or 0.7m2/ g or smaller.
Conductive material be or including silver in the case of, silver powder can be suitably used.Suitable silver powder is554-2。
In general, in some embodiments, including the particle of the basic crystalline state of one or more metal oxides or by it
The inorganic particle mixture of composition be solid portion ingredient in there is the ingredient of time highest content.
Solid portion may include one or more other additive materials, such as 0 to the 10 weight weights of % or 0 to 5
Measure the other additive material of %.
Organic media
The solid portion of the electroconductive paste of the present invention is dispersed in organic media.Organic media may be constructed such as electroconductive paste
At least 2 weight %, at least 5 weight % or at least 9 weight %.Organic media may be constructed the 20 weight % or less of electroconductive paste,
15 weight % or less, 13 weight % or less or 10 weight % or less.
It is therefore to be understood that solid portion may be constructed at least 80 weight % of electroconductive paste, at least 85 weight %,
At least 87 weight % or at least 90 weight %.Solid portion may be constructed the 98 weight % or less of electroconductive paste, 95 weight % or
Less or 91 weight % or less.
Organic media generally comprises the organic solvent for wherein dissolving or being dispersed with one or more additives.Such as this field skill
Art personnel will readily appreciate that, generally select the component of organic media to provide suitable consistency and rheological property, to allow
Electroconductive paste is printed onto in semiconductor substrate, and is transporting and paste is made to keep stablizing in storing process.
The example of suitable solvent for organic media includes selected from butyldiglycol, butyldiglycol acetic acid esters, terpin
Alcohol, two aklylene glycol alkyl ethers (such as diethylene glycol dibutyl ether and Tripropylene glycol monomethyl Ether), ester alcohol are (such as)、
One or more solvents of 2- (2- methoxy propoxies) -1- propyl alcohol and its mixture.
The example of suitable additive includes those dispersants, and to help solid portion to be dispersed in paste, viscosity/rheology changes
Property agent, thixotropic modifier, wetting agent, thickener, stabilizer and surfactant.
For example, organic media can include selected from rosin (kollophonium resins), acrylic resin (such as), the alkylammonium salt of polycarboxylic acid polymers (such as110 or 111), polyamide wax (such as
Thixatrol Or Thixatrol), nitrocellulose, ethyl cellulose, hydroxypropyl cellulose and lecithin
Fat it is one or more.
In general, by the way that the component of conductive material, the component of inorganic particle mixture and organic media is mixed in any order
It is combined to prepare electroconductive paste.
The manufacture of surface electrode and solar cell
Appropriate method familiar to the person skilled in the art for manufacturing the surface electrode of solar cell.Similarly, ability
Field technique personnel are familiar with the appropriate method for manufacturing solar cell.
The method of surface electrode for manufacturing solar cell is generally comprised is applied to semiconductor substrate by electroconductive paste
On surface and fire applied electroconductive paste.
Electroconductive paste can be applied by any suitable method.For example, can by print for example by silk-screen printing or
Ink jet printing applies electroconductive paste.Electroconductive paste can apply on a semiconductor substrate to form the optical receiving surface of solar cell
Electrode.Alternatively, electroconductive paste can apply on a semiconductor substrate to form the back surface electrode of solar cell.Solar-electricity
Pond can be N-shaped or p-type solar cell.Paste can be applied to N-shaped emitter (in p-type solar cell) or p-type hair
On beam (in N-shaped solar cell).Some solar cells are referred to as carrying on the back junction battery.In such a case, it is possible to it is preferred that
The electroconductive paste of the present invention is applied to the back surface of the semiconductor substrate of solar cell.Similar to being applied to solar cell
Optical receiving surface anti-reflection coating, this back surface is typically covered with insulating passivation layer (such as SiN layer).Alternatively, leading
Electricity paste can be applied to thin-film solar cells or electroconductive paste can be applied to the electronic device in addition to solar cell
Substrate.
Those skilled in the art know the appropriate technology for firing the electroconductive paste applied.Fig. 1 shows illustrative burning
Koji-making line.Common sintering procedure lasts about 30s, and electrode surface reaches about 800 DEG C of peak temperature.In general, furnace temperature can higher
To reach this surface temperature.Firing can for example continue 1 hour or less, 30 minutes or less, 10 minutes or less or 5 points
Clock is less.Firing can continue at least 10s.For example, the peak surface temperature of electrode can be 1200 DEG C or lower, 1100 DEG C
Or it is lower, 1000 DEG C or lower, 950 DEG C or lower, 900 DEG C or lower, 800 DEG C or lower or 750 DEG C or lower.Electrode
Peak surface temperature can be at least 500 DEG C or at least 600 DEG C.
The semiconductor substrate of electrode can be silicon substrate.For example, it can be single crystal semiconductor substrate or poly semiconductor
Substrate.The substrate of replacement includes CdTe.Semiconductor may, for example, be p-type semiconductor or n-type semiconductor.
Semiconductor substrate can include insulating layer on the surface thereof.The electroconductive paste of the present invention is usually applied to insulating layer
To form electrode on top.In general, insulating layer will be non-reflective.Suitable insulating layer is SiNx (such as SiN).Other are suitable
Insulating layer include Si3N4、SiO2、Al2O3And TiO2。
Method for manufacturing p-type solar cell can include to be applied to back side electroconductive paste (such as comprising aluminium) partly to lead
The surface of body substrate, and back side electroconductive paste is fired to form backside electrode.Usually back side electroconductive paste is applied to and receives table with light
The opposite semiconductor substrate face of face electrode.
In general, in manufacturing p-type solar cell, back side electroconductive paste is applied to the back side of semiconductor substrate, and (non-light connects
Receive side) and it dries on substrate, positive side electroconductive paste is applied to the positive side (light-receiving side) of semiconductor substrate later and in substrate
Upper drying.Alternatively, positive side paste can be applied first, pasted with after-applied back side.Usually electroconductive paste cofiring system (is fired to have and be applied
It is added on the substrate of its positive side and both back side pastes), to form the solar cell for including positive side and back side conductive trace.
The efficiency of solar cell can be improved by providing passivation layer in the back side of substrate.Suitable material includes
SiNx (such as SiN), Si3N4、SiO2、Al2O3And TiO2.The region of usual passivation layer is partially removed (such as is burnt by laser
Erosion) to allow the contact between semiconductor substrate and back side conductive trace.Alternatively, in the feelings that the paste of the present invention is applied to back side
Under condition, paste can play the role of etch passivation layer and enable to form electrical contact between semiconductor substrate and conductive trace.
In the case where forming conductive trace on the substrate other than the semiconductor substrate for solar cell, to substrate
The mode for applying electroconductive paste is not particularly limited.For example, electroconductive paste can be printed onto on substrate (such as ink jet printing or silk screen
Printing), or (such as dip-coating) can be coated on substrate.Firing condition is also not particularly limited, but can with above
Condition is similar those of described in surface electrode about formation for solar cell.
In the case of this paper specified ranges, it is intended that each endpoint of range is independent.Therefore, it is expressly contemplated that range
Each of the upper extreme point enumerated can independently be combined with each lower extreme point enumerated, vice versa.
Embodiment
Frit and inorganic blend
Frit and inorganic blend are prepared using marketable material.The composition of frit and inorganic blend is in the following table 1,2
With 3 in provide.
Table 1- frits form
(the weight % based on oxide and mole % compositions)
The inorganic blend compositions of table 2-
(the weight % compositions based on oxide)
| Composition | TeO2 | Li2CO3 | Bi2O3 | Bi5O(OH)9(NO3)4 | ZnO | CeO2 | Na2CO3 | MoO3 | |
| A | Weight % | 39.4 | 5.5 | 0 | 40.1 | 2.6 | 10.1 | 1.5 | 0.9 |
| B | Weight % | 42.8 | 5.9 | 34.8 | 0 | 2.9 | 11.0 | 1.6 | 1.0 |
| C | Weight % | 87.9 | 12.1 | 0 | 0 | 0 | 0 | 0 | 0 |
| D | Weight % | 51.3 | 7.1 | 41.7 | 0 | 0 | 0 | 0 | 0 |
| E | Weight % | 49.5 | 6.8 | 40.3 | 0 | 3.4 | 0 | 0 | 0 |
| F | Weight % | 49.0 | 6.8 | 39.8 | 0 | 3.3 | 0 | 0 | 1.1 |
The inorganic blend compositions of table 3-
(the weight % compositions based on oxide)
Glass is manufactured according to following standardization program.Use the raw material of laboratory blender hybrid glass.By 100g mixtures
It is melted in ceramic crucible, in Carbolite furnace for testing room.The crucible for accommodating raw mixture is placed in stove, together
When keep cooling, the thermal shock to avoid ceramic crucible and cracking.Fusing carries out at 1000-1200 DEG C in air.It will melt
Melt glass to be quenched in water to obtain frit.Frit is dried overnight at 120 DEG C in heating room, then in planetary mill
Wet-milling is to provide the D having less than 2 μm in machine90The particle of particle size (using Malvern Mastersizer 2000 and makes
It is measured with laser diffraction method).Wet-milling can carry out in organic solvent or water.Glass powder is dry in pan dryer
And it is sieved.
Inorganic blend A to L is prepared by using laboratory blender mixed oxide, carbonate and nitrate with life
Mixing material is produced, is followed by that wet-milling is co-mulled and made into material to produce in butyldiglycol by mixing material.Grinding condition is listed in down
In table 4.Then gained blending powder is dried and is sieved in pan dryer.
Using with the identical formulas of composition A and raw material, by grind one by one individual component and then by their combinations with
Inorganic blend is formed to prepare other inorganic blend A1 and A2.A1 passes through each oxide of wet-milling, carbonate and nitric acid respectively
Salt is followed by pan dryer the dry component each ground one by one.Then use laboratory blender by gained dry powder
It combines and homogenizes to produce inorganic blend A1.
By each oxide of wet-milling, carbonate and nitrate respectively, it is followed by the slurry that mixing is obtained by wet-milling each component
To prepare inorganic blend A2.The slurry of obtained mixing is homogenized using laboratory blender, then in pan dryer
Drying is to form inorganic blend A2.
X-ray diffraction analysis
It (is being ground using the sample for forming B as mixing material (i.e. before above-mentioned grinding steps) and as material is co-mulled and made into
After mill step) carry out X-ray diffraction (XRD) analysis.XRD analysis is a kind of angle for by measuring these diffracted beams
The tool of the atomic and molecular structure of crystal is identified with intensity.Fig. 2 and 3 respectively illustrates the mixing material of composition B and grinds altogether
Grind the analysis of material.
The result shows that mixing material includes the oxide and carbonic acid of tellurium, cerium, bismuth and zinc in crystalline starting material is now corresponded to
The a large amount of peak (Fig. 2) of lithium.Grinding-material diffraction pattern includes less peak and 25 ° and 35 ° of halation pattern.Halation pattern table
Possible decrystallized (' X-ray amorphous material) of bright material (or part of material).It is recognizable to correspond to tellurium, bismuth and cerium
Crystalline oxide peak.
X-ray diffraction (XRD) is carried out to the sample of inorganic blend A2 to analyze.The analysis of inorganic blend A2 is shown in Fig. 4
In.
The result shows that inorganic blend A2 includes the oxide and carbon of tellurium, cerium, bismuth and zinc in crystalline starting material is now corresponded to
The a large amount of peak (Fig. 4) of sour lithium.
Hot stage microscope is analyzed
Thermal station microscopy (HSM) is for measuring the Yi Rongxing of melting behaviors, weld point, softening point, fusing point and profit on substrate
The effective technology of wet behavior.This method is for comparing glass composition and inorganic blend.Use crystalline silicon solar piece
As substrate to observe wetability of the material on the solar cell containing anti-reflection coating (ARC), and observe glass/nothing
Possibility between machine blend and ARC layer is reacted.The flow behavior that HSM is shown shows how material will flow in paste, display
In true solar cell sintering procedure will there is a situation where trend.
It is comparative to form A and there is the comparison between bismuth oxide and the inorganic blend variant (composition A and B) of nitrous acid bismuth
It is shown in Fig. 5.Expansion is presented at about 350 DEG C for glass, this is attributable to redox reaction and is happened in glass matrix, and works as
Softening point occurs at about 600 DEG C when flowing starts.
Inorganic blend (composition A) containing nitrous acid bismuth starts to be sintered (decomposition of nitrous acid bismuth) at about 260 DEG C, and
Flowing starts from the flowing temperature of glass (comparative composition A) about 100 DEG C, at about 700 DEG C.B is formed with much lower
About 400 DEG C of flowing temperature.
Further HSM experiments are carried out by simplifying original inorganic blend composition, as shown in Figure 6.It tests in table 2
The composition as composition C, D, E and F.From the point of view of the result found, Te-Li, Te-Li-Bi, Te-Li-Zn-Bi and Te-
The combination of Li-Zn seems to contribute to solar cell metallization good flow behavior of concern in lesser degree.
It pastes standby
It is organic using the commercially available silver powder of 88 weight %, the inorganic blend of 2 weight % or 1.5 weight %, the standard of surplus
Medium prepares the conductive silver paste of the inorganic particle mixture comprising basic crystalline state.Abrasive inorganic blend group at different conditions
Object is closed to provide different particle size distributions.The particle size distribution (PSD) and lapping stick of inorganic blend are described in table 4
Part.Wet grinding is carried out in butyldiglycol.
After grinding, inorganic particle mixture is dried and is sieved in pan dryer.(such as made using laser diffractometry
With Malvern Mastersizer 2000) measure particle size.Also use commercially available silver powder, the 2 weight % glass of 88 weight %
Expect, the standard organic media of surplus prepares comparative conductive silver paste.By being pre-mixed all components and in three-roll grinder
By for several times paste is prepared to generate uniform paste.Viscosity is adjusted by adding medium or solvent, in 100s-1Shearing speed
Rate has similar value.The composition of the paste in being formed for following solar cells is given in table 5.
Table 4- glass and inorganic blend particle size distribution
(being measured using Malvern Mastersizer 2000)
Table 5- electroconductive pastes form
(weight % compositions)
Solar cell is formed
On the back side of the polycrystalline silicon wafer of sheet resistance, 6 inches of sizes with 90 Ω/ silk is carried out with commercially available aluminium paste
Wire mark brush is dried in IR Mass belt dryers and is grouped at random.Silk is carried out with positive side silver paste to each group in these groups
Wire mark brush, the positive side silver paste are one of the electroconductive pastes for being described herein and illustrating in more detail above.
Silk screen for positive side paste is open (finger opening) with 50 μm of finger.It, will be electric after printing positive side
It dries in IR Mass belt dryers and is fired in Despatch band ovens in pond.There are six with upper for Despatch stoves
The firing area in portion and lower heater.First three area is programmed for about 500 DEG C, so as to the burning-off adhesive from paste, the 4th and the 5th
Area is in higher temperature, has 945 DEG C of maximum temperature (furnace temperature) in final area.The furnace zone speed of the experiment is 610cm/
min.The temperature of record measures the temperature at solar cell surface to determine by using thermocouple in sintering procedure.The sun
Temperature at energy battery surface is no more than 800 DEG C.This is made to contain the typical paste with the glass of about 600 DEG C of softening points
Typical firing temperature., it is surprising that observed for the inorganic particle mixture of the crystalline state of the present invention this good
Good flow behavior and contact is formed.
After cooling, it is being that test is fired too in the I-V curve tracer of cetisPV-CTL1 from Halm, model
Positive energy battery.By I-V curve tracer, result is provided by directly measuring or being calculated using internal software.
(in order to make the influence of contact area minimize, in each individual test group using identical printing screen and
The pastes of identical viscosities prepares battery.Which ensure that the line width of the paste compared is essentially identical and does not influence to measure.)
Solar cell properties
Fill factor indicates performance of the solar cell relative to theoretic ideal (0 resistance) system.Fill factor with
Contact resistance correlation-contact resistance is lower, and fill factor can be higher.But if the inorganic additive of electroconductive paste excessively aggressivity,
The pn-junction of semiconductor may then be damaged.In this case, contact resistance can be low, but due to the damage (complex effect of pn-junction
With lower shunt resistance), it may appear that lower fill factor.Therefore, high fill factor shows silicon wafer and conductive trace
Between there are low contact resistances, and the firing of paste on the semiconductor have no adverse effect semiconductor pn-junction (that is, shunting
Resistance is high).
The quality of pn-junction can be determined by measuring pseudo- fill factor (SunsVocFF).This be with due in battery
Unrelated fill factor is lost caused by resistance.Therefore, contact resistance is lower, and SunsVoc FF are higher, obtained filling system
Number will be higher.Method familiar to the person skilled in the art for determining SunsVoc FF, such as described in bibliography 1
's.SunsVoc FF are measured in the open circuit condition, and unrelated with series resistance effect.
η represents the efficiency of solar cell, and the solar energy of input is compared with the electric energy of output.It is small in terms of efficiency
Variation can be very valuable in commercial solar cell.
185 results of table 6- solar cell tests PV
241 results of table 7- solar cell tests PV
Table 8- solar cell test PV results
Corresponding PSD data in the result and table 4 of comparison sheet 6, it could be assumed that:The particle size distribution of inorganic blend
Having on final battery performance with uniformity influences.
It is shown between intermediate value efficiency (η) and maximal efficiency (η max) for example, pasting 1382BC made of the paste of embodiment 7
Go out than the variation with more little particle and the material bigger evenly changed.
Shown in comparison sheet 8 as a result, it could be assumed that:The mode for preparing inorganic oxide mixture can be to final electricity
Pond performance has influence.
Specific contact resistivity
Further test is carried out using TLM methods to measure specific contact resistivity (table 10).
Use the silver powder of 87.5 weight %, the inorganic blend powder (composition is referring to table 8) and organic media of 2.5 weight %
To prepare conductive silver paste.
For these tests, Turbula mixing 30min are carried out to inorganic blending compositions, then with 3000rpm, 30s
The powder that 10g is mixed and 10g ZrO22mm balls quickly mixing twice.
Then use rapid heat-treatment furnace to coating Si3N4Silicon wafer on printing contact be fired.Sintering procedure is non-
Often short, temperature range is 600-650 DEG C, and time range is 30-60s, the pn-junction of the silver paste and silicon wafer printed during this period it
Between generate contact.
Inorganic blend composition used in being listed in table 9.
The inorganic blend compositions of table 9-
(the weight % compositions based on oxide)
| Composition | TeO2 | Li2CO3 | Bi2O3 | ZnO | Na2CO3 | MoO3 | |
| M | Weight % | 48.2 | 6.7 | 39.1 | 3.2 | 1.8 | 1.0 |
| N | Weight % | 48.7 | 6.7 | 39.6 | 3.2 | 1.8 | 0 |
| O | Weight % | 49.7 | 6.9 | 40.4 | 0 | 1.9 | 1.1 |
| P | Weight % | 50.3 | 7.0 | 40.8 | 0 | 1.9 | 0 |
Table 10-Si3N4The specific measuring contact resistance of silver contact on/Si chips.Silver paste contains silver and 2.5
The composition M-P as inorganic blend of weight %.
Composition M and N provide the specific contact resistance of excellent silver contact.Seem that the firing temperature being also improved improves
The general trend of specific contact resistivity.It can be seen that from specific contact resistance value and containing Li2CO3、Na2CO3、Bi2O3And TeO2's
Inorganic blend is (presence or absence of MoO3) in, the presence (composition M and N) of ZnO seems to improve the electric conductivity of contact.
Bibliography
1.A.McEvoy, T.Markvart, L.Castaner.Solar cells:Material, Manufacture and
Operation.Academic Press, second edition, 2013.
Claims (38)
1. a kind of electroconductive paste for forming conductive trace or coating on substrate, which includes being dispersed in consolidating in organic media
Body portion,
The solid portion includes conductive material and inorganic particle mixture；
The wherein described inorganic particle mixture include two or more different metal compounds basic crystalline state particle and
It is substantially free of lead；And the glass content of the wherein described solid portion is less than 1 weight %.
2. electroconductive paste according to claim 1, wherein each in described two or more different metallic compounds
Kind only includes a kind of metallic element.
3. electroconductive paste according to claim 1 or 2, wherein the glass content of the solid portion is less than 0.5 weight %, it is excellent
Choosing is less than 0.25 weight %, more preferably less than 0.05 weight %, more preferably less than 0.01 weight %.
4. electroconductive paste according to any one of claim 1 to 3, wherein the solid portion is substantially free of glass.
5. electroconductive paste according to any one of the preceding claims, wherein the inorganic particle mixture includes being less than 0.1
The PbO of weight %, preferably smaller than 0.05 weight %, more preferably less than 0.01 weight %, more preferably less than 0.005 weight %'s
PbO。
6. electroconductive paste according to any one of the preceding claims, wherein the inorganic particle mixture includes tellurium compound
And lithium compound.
7. electroconductive paste according to any one of the preceding claims, is substantially free of lead.
8. electroconductive paste according to any one of the preceding claims, wherein the conductive material include selected from silver, copper, nickel and
One or more metals in aluminium.
9. electroconductive paste according to claim 8, wherein the conductive material includes silver.
10. electroconductive paste according to claim 8, wherein the conductive material is made of silver.
11. electroconductive paste according to any one of the preceding claims, wherein the ingredient in being present in the solid portion
In, the ingredient of highest content is conductive material, and the ingredient of secondary highest content is inorganic particle mixture.
12. electroconductive paste according to any one of the preceding claims, wherein the solid portion includes 0.1 to 15 weight %
Inorganic particle mixture.
13. electroconductive paste according to any one of the preceding claims, wherein the solid portion includes 80 to 99.9 weights
Measure the conductive material of %.
14. electroconductive paste according to any one of the preceding claims, wherein the particle of the inorganic particle mixture has
Wherein it is applicable in one or more particle size distributions of the following conditions:
(a)D10≤0.41μm；
(b)D50≤1.6μm；
(c)D90≤4.1μm；
(d)(D50–D10)≤1.15μm；
(e)(D90–D50)≤2.5μm；
(f)(D90–D10)≤3.7μm；Or
(g)(D50/D10)≤3.85。
15. a kind of electroconductive paste for forming conductive trace or coating on substrate, the paste includes to be dispersed in organic media
Solid portion,
The solid portion includes conductive material and inorganic particle mixture；
The wherein described inorganic particle mixture includes with two or more the particle size point for being wherein applicable in the following conditions
The particle of the basic crystalline state of cloth:
(a)D10≤0.41μm；
(b)D50≤1.6μm；
(c)D90≤4.1μm；
(d)(D50–D10)≤1.15μm；
(e)(D90–D50)≤2.5μm；
(f)(D90–D10)≤3.7μm；With
(g)(D50/D10)≤3.85。
16. the electroconductive paste according to claims 14 or 15, wherein the particle of the inorganic particle mixture meets condition
(a)。
17. according to the electroconductive paste described in any one of claim 14-16, wherein the particle of the inorganic particle mixture meets
Condition (b).
18. according to the electroconductive paste described in any one of claim 14-17, wherein the particle of the inorganic particle mixture meets
Condition (c).
19. according to the electroconductive paste described in any one of claim 14-18, wherein the particle of the inorganic particle mixture meets
Condition (d).
20. according to the electroconductive paste described in any one of claim 14-19, wherein the particle of the inorganic particle mixture meets
Condition (e).
21. according to the electroconductive paste described in any one of claim 14-20, wherein the particle of the inorganic particle mixture meets
Condition (f).
22. according to the electroconductive paste described in any one of claim 14-21, wherein the particle of the inorganic particle mixture meets
Condition (g).
23. according to the electroconductive paste described in any one of claim 14-22, wherein the particle of the inorganic particle mixture meets
D90≤2.2μm。
24. according to the electroconductive paste described in any one of claim 14-23, wherein the particle of the inorganic particle mixture meets
D50≤1.05μm。
25. according to the electroconductive paste described in any one of claim 14-24, wherein the particle of the inorganic particle mixture meets
D10≤0.4μm。
26. according to the electroconductive paste described in any one of claim 14-25, wherein the particle of the inorganic particle mixture meets
D90-D10≤1.8μm。
27. according to the electroconductive paste described in any one of claim 14-26, wherein the particle of the inorganic particle mixture meets
D90-D50≤1.15μm。
28. according to the electroconductive paste described in any one of claim 14-27, wherein the particle of the inorganic particle mixture meets
D50–D10≤0.6μm。
29. according to the electroconductive paste described in any one of claim 15-28, wherein the particle of the basic crystalline state is two kinds or more
The particle of the basic crystalline state of a variety of different metal compounds.
30. according to the electroconductive paste described in any one of claim 15-29, wherein the inorganic particle mixture is substantially free of
Lead.
31. according to the electroconductive paste described in any one of claim 15-30, wherein the glass content of the solid portion is less than 1
Weight %.
32. a kind of method preparing the electroconductive paste according to any one of claim 1-31, including mixing in any order
The component of organic media, conductive material and inorganic particle mixture.
33. according to the method for claim 30, being included in particle and the institute of the basic crystalline state of the inorganic particle mixture
The particle of the basic crystalline state of the inorganic particle mixture is co-mulled and made into before stating organic media and conductive metal mixing.
The organic media, the conductive material and described inorganic are mixed 34. according to the method for claim 30, being included in
The each component of the inorganic particle mixture is ground before the component of granulate mixture respectively.
35. a kind of manufacturing method of the surface electrode of solar cell, the method includes by any one of claim 1-31
Defined by electroconductive paste be applied to semiconductor substrate and fire applied electroconductive paste.
36. a kind of electrode for solar cell, the electrode includes the conductive trace in semiconductor substrate, wherein described lead
Electric trace is pasted as defined by any one of claim 1-31 by firing on the semiconductor substrate and obtains or can obtain
.
37. a kind of solar cell, including the surface electrode as defined by claim 36.
38. use of the electroconductive paste in the surface electrode of manufacture solar cell according to any one of claim 1-31
On the way.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011016151.8A CN112102980A (en) | 2015-11-13 | 2016-11-08 | Conductive paste and conductive track or coating |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1520060.3 | 2015-11-13 | ||
| GBGB1520060.3A GB201520060D0 (en) | 2015-11-13 | 2015-11-13 | Conductive paste and conductive track or coating |
| PCT/GB2016/053484 WO2017081448A1 (en) | 2015-11-13 | 2016-11-08 | Conductive paste and conductive track or coating |
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|---|---|---|---|
| CN202011016151.8A Division CN112102980A (en) | 2015-11-13 | 2016-11-08 | Conductive paste and conductive track or coating |
Publications (2)
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|---|---|
| CN108352211A true CN108352211A (en) | 2018-07-31 |
| CN108352211B CN108352211B (en) | 2020-10-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011016151.8A Pending CN112102980A (en) | 2015-11-13 | 2016-11-08 | Conductive paste and conductive track or coating |
| CN201680065684.0A Expired - Fee Related CN108352211B (en) | 2015-11-13 | 2016-11-08 | Conductive paste and conductive track or coating |
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|---|---|
| US (2) | US10868200B2 (en) |
| EP (2) | EP3731241A1 (en) |
| KR (1) | KR20180082517A (en) |
| CN (2) | CN112102980A (en) |
| GB (1) | GB201520060D0 (en) |
| TW (2) | TWI637402B (en) |
| WO (1) | WO2017081448A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112334423A (en) * | 2018-07-24 | 2021-02-05 | 庄信万丰股份有限公司 | Particulate mixture, kit, ink, method and article |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB202005268D0 (en) | 2020-04-09 | 2020-05-27 | Johnson Matthey Plc | Method of forming glass coatings and glass coated products |
| GB202007908D0 (en) | 2020-05-27 | 2020-07-08 | Johnson Matthey Plc | Conductive pastes for solar cells |
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- 2016-11-08 CN CN201680065684.0A patent/CN108352211B/en not_active Expired - Fee Related
- 2016-11-08 EP EP16794017.0A patent/EP3374998B1/en active Active
- 2016-11-11 TW TW105136820A patent/TWI637402B/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
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| TW201732840A (en) | 2017-09-16 |
| TW201731791A (en) | 2017-09-16 |
| US10868200B2 (en) | 2020-12-15 |
| US20180351014A1 (en) | 2018-12-06 |
| GB201520060D0 (en) | 2015-12-30 |
| EP3374998B1 (en) | 2020-07-01 |
| WO2017081448A1 (en) | 2017-05-18 |
| KR20180082517A (en) | 2018-07-18 |
| CN112102980A (en) | 2020-12-18 |
| US20210050462A1 (en) | 2021-02-18 |
| EP3731241A1 (en) | 2020-10-28 |
| TWI657065B (en) | 2019-04-21 |
| TWI637402B (en) | 2018-10-01 |
| CN108352211B (en) | 2020-10-13 |
| EP3374998A1 (en) | 2018-09-19 |
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